TR201909253T4 - The process of making graphene-containing viscose fibers. - Google Patents

The process of making graphene-containing viscose fibers. Download PDF

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TR201909253T4
TR201909253T4 TR2019/09253T TR201909253T TR201909253T4 TR 201909253 T4 TR201909253 T4 TR 201909253T4 TR 2019/09253 T TR2019/09253 T TR 2019/09253T TR 201909253 T TR201909253 T TR 201909253T TR 201909253 T4 TR201909253 T4 TR 201909253T4
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graphene
viscose
cellulose
acid
nitrate
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Tang Yilin
Jiang Chengzhen
Gao Shaofeng
Zhang Jinzhu
XU Ripeng
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Jinan Shengquan Group Share Holding Co Ltd
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof
    • D01F2/06Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof from viscose
    • D01F2/08Composition of the spinning solution or the bath
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B9/00Cellulose xanthate; Viscose
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/184Preparation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00Carbon; Compounds thereof
    • C01B32/15Nano-sized carbon materials
    • C01B32/182Graphene
    • C01B32/194After-treatment

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  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
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  • Artificial Filaments (AREA)
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  • General Life Sciences & Earth Sciences (AREA)
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Abstract

Mevcut buluş, grafen içerikli bir viskoz lif ve bunun hazırlanış yöntemi ile ilgilidir, burada grafen, 10 katmandan daha fazla olmayan oksidize edilmemiş bir grafendir. Hazırlama yöntemi, çekme öncesinde bir viskoza bir grafen eklenmesini içerir. Mevcut buluşa göre elde edilen viskoz lif, önemli ölçüde uzak kızılötesi ve antibakteriyel özelliklere sahiptir.The present invention relates to a graphene-containing viscose fiber and its method of preparation, wherein the graphene is an unoxidized graphene with no more than 10 layers. The preparation method involves adding a graphene to a viscose prior to drawing. The viscose fiber obtained according to the present invention has substantial far infrared and antibacterial properties.

Description

TARIFNAME GRAFEN IÇERIKLI VISKOZ LIFLERIN YAPIM PROSESI Teknik Saha Mevcut bulus, bir viskoz lif ve bunun hazirlanisina yönelik proses ve özellikle bir grafen Viskoz lif ve bunun hazirlanisina yönelik proses ile ilgilidir. Teknigin Alt Yapisi Viskoz lif genel olarak, oldukça yüksek bir selüloz safligina sahip bir çözme hamuru hazirlamak üzere pisirme, agartma ve benzeri bir dizi prosese tabi tutulan ve akabinde emprenye, sikistirma, ezme, eskitme, ksantasyon, çözme, karistirma, filtreleme, köpükten arindirma, filtreleme, çekme, ileri islem, kurutma, ambalajlama ve benzeri gibi çalisma kesimlerini gören ham materyaller Iinter, misir koçani, ahsap ve az miktarda bambu ve benzeri gibi dogal selülozlar ile hazirlanir. Mevcut durumda Viskoz lif çogunlukla tekstil lifi olarak kullanilir. CN 103046151 A, oksidize edilmis bir grafen solüsyonu ile islah edilmis bir selüloz solüsyonunun karistirilmasi, karisimin Viskoz bir yas çekim prosesi vasitasiyla kaliplanmasi ve akabinde karisimin indirgenmesi yoluyla hazirlanan, grafen harmanli olarak islah edilmis bir selüloz lif açiklar. Bu yöntem ile elde edilen VISkOZ lif, mukavemet açisindan az ölçüde daha gelismistir ve bunun kuru kirilma mukavemeti, 2.62 cN/dtex'e kadar olabilir ve islak kirilma mukavemeti, 1.54 cN/dtex*e ulasir. Ayrici bununla ilgili olarak açiklanan içerikler, grafenin lif mukavemetini arttirma etkisini gösterir. CN 103556275 A, uzak kizilötesi bir bambu kömürü VISkOZ lif ve bunun hazirlanis yöntemini açiklar. Mevcut teknikte bulunmayan uzak kizilötesi bambu kömürü Viskoz lif gelistirmek ve bambu kömürü VISkOZ Iifin zayif çekilebilirlik problemini ele almak üzere mevcut bulus, uzak kizilötesi bir seramik tozunun içeriginin agirlikça %1-10, bir bambu kömürünün içeriginin agirlikça %O.1-10, uzak kizilötesi yayma kuvvetinin %80'den daha büyük olmasi, amonyak absorpsiyon hizinin %50'den daha düsük olmamasi, geçirgenligin 500 mm/s'den daha düsük olmamasi ve yikamaya karsi renk hasliginin 4- derecesinde olmasi ile karakterize edilen Iifin, uzak kizilötesi bir bambu kömürü viskoz lif ile bunun hazirlanis yöntemini saglar. Mevcut bulus, isi izolasyonu etkilerine sahip olan uzak kizilötesi bambu kömürü viskoz lif ile birlikte ayni zamanda hücre dokularini aktive etme ve kan dolasimini ilerletme gibi sagliksal islevlere sahip olan isinimli uzak kizil ötesi isinlari sunar. Ayrica açiklanan bu içerikler, uzak kizil ötesi etkilerin, seramik tozu eklenerek elde edildigini gösterir. CN 104151515 A, formaldehit, furfuril alkol ve grafenin reakte edilmesi ile hazirlanan grafen modifiyeli bir furan reçine açiklar. Bulus, grafen modifiyeli furan reçinesinin hazirlanis yöntemini saglar. Bulusun sagladigi grafen modifiyeli furan reçinesi, yüksek bir baglanma mukavemetine sahiptir; ve grafen içerisindeki karbon atomlarinin arasindaki baglanti oldukça esnektir, bu sekilde bulusun sagladigi grafen modifiyeli furan reçinesi yüksek bir dayanima sahiptir. CN 103966844 A, grafen bir elektrik iletimli kompozit lifin hazirlanis yöntemini açiklar. Hazirlanis yöntemi basittir, proses içinde kabul edilebilirdir ve uygulanmasi kolaydir. Bu yöntem ile hazirlanan grafen elektrik iletimli kompozit lif, yüksek bir indirgeme ölçüsü ile birlikte yüksek bir iletkenlik ve anti-radyasyon performansi sergileyen bir verim ile elde içeren grafen esasli iletken bir kompozit lif açiklar. Ayni zamanda bu liflerin hazirlanis prosesleri ve bunlarin kullanimlari saglanir. Bulusun Açiklamasi Mevcut bulus, yeni bir viskoz lif ile viskoz lifin antibakteriyel ve bakteriyostatik özellikleri ile birlikte uzak kizilötesi fonksiyonlarini daha fazla gelistirecek sekilde bir hazirlanis yöntemi saglar. Mevcut bulusa göre, bir viskoz lifin hazirlanis yöntemi sunlari içerir: viskoz veya yari islenmis bir viskoz ürününe 10 katmandan daha fazla olmayan bir grafen eklenmesi, burada grafen, asagidaki adimlari içeren bir yöntem ile hazirlanir: 1) Iignoselülozlar elde etmek üzere misir koçanlarinin inorganik asidik bir aköz solüsyon içinde hidrolize edilmesi; 2) gözenekli selülozlar saglamak üzere Iignoselülozlarin bir isleme ajani ile 70 °C-180 °C'de islenmesi, burada kullanilan isleme ajani, bir asit, asit sülfit veya alkali sülfittir; 3) gözenekli selülozlarin, ferrik klorid, ferröz klorid, ferrik nitrat, ferröz nitrat, ferrik sülfat, ferröz sülfat, potasyum ferrisiyanür, potasyum ferrosiyanür, potasyum trioksalatoferrat, kobalt klorid, kobalt nitrat, kobalt sülfat, kobalt asetat, nikel klorid, nikel nitrat, nikel sülfat ve nikel asetattan olusan grup içinden seçilen bir katalizör ile islenmesi, burada bir isleme sicakligi 50 °C-150 4) önceki adimda elde edilen gözenekli selülozlarin, bir grafen prekürsörü saglayacak termal izolasyona yönelik olarak oksijensiz bir ortamda arka arkaya 1000 °C'ye yerlestirilmesi; ) nihai ürün olan grafeni elde etmek üzere grafen prekürsörünün sirasiyla olmak üzere alkali, asit ve su ile yikanmasi. Tercihen yöntemdeki 2) adimi, kullanilan isleme ajani, sülfürik asit, kalsiyum hidroksit, sodyum hidroksit, amonyum hidroksit veya magnezyum hidroksit, kalsiyum sülfit, magnezyum sülfit, sodyum sülfit veya amonyum sülfitten olusan grup içinden seçilir. Tercihen eklenen grafen miktari, viskoz içindeki a-selüloz kütlesinin %0.05-1.0'i, daha çok tercihen viskoz içindeki oi-selüloz kütlesinin %0.2-0.8'idir. Grafenin hazirlanisina yönelik olarak mevcut bulusta kullanilan ham materyaller, biyokütleden derive edilir ve biyokütle kaynaklari, sebzeleri ve/veya tarim ve ormancilik atiklarinin herhangi biri veya bunlarin en az ikisinin bir kombinasyonu içinden seçilir, tercihen igne yaprakli agaç, genis yaprakli agaç, yaprakli agaçtan herhangi biri ile tarim ve ormancilik atiklari veya bunlarin en az ikisinin bir kombinasyonu içinden seçilir; tarim ve ormancilik atiklari tercihen misir sapi, misir koçani, süpürge darisi sapi, seker pancari küspesi, bagas, furfural kalintisi, ksiloz kalintisi, biçki talasi, pamuk sapi, kabugu ve kamisi veya bunlarin en az ikisinin bir kombinasyonu ve tercihen mevcut durumda halka açik olarak satilan misir koçani içinden seçilir. Biyokütle ham materyalleri, özellikle misir koçanindan hazirlanan grafen, mikrokozmik düzeyde gözeneklilik sergiler, bu sekilde spesifik yüzey alani, özelikle basvuru sahibi tarafindan hazirlanan grafen durumunda artmis hale gelir. Tercih edilebilir bir düzenlemede viskozun hazirlanmasi, emprenye, sikistirma, ezme, eskitme, ksantasyon, çözme, olgunlastirma, filtreleme ve köpükten arindirma adimlarini içerir, burada grafen, filtreleme öncesinde eklenir. Ayrica grafen ilk olarak, bir dagilma sistemi içine hazirlanir, burada dagitici solvent sudur ve dagilma sisteminin kati içerigi, %O.1-1'dir. Tercih edilebilen bir diger düzenlemede viskozun hazirlanmasi, emprenye, sikistirma, ezme, eskitme, ksantasyon, çözme, olgunlastirma, filtreleme ve köpükten arindirma adimlarini içerir, burada grafen, çözme adimi sirasinda eklenir ve grafen, selüloz ksantatlari çözmek üzere kullanilan seyreltik bir alkalin sölüsyonu içinde önceden dagitilir. Mevcut bulus ayrica, bir grafen içeren bir viskoz lif ile ilgilidir, burada grafen, oksidize edilmis bir grafen degildir. Oksidize edilmemis grafen spesifik olarak, hazirlanmamis ve bir oksidasyon indirgeme yöntemi ile elde edilmemis grafen veya hazirlanis prosesi bir oksidizasyon adimi içermeyen grafen anlamina gelir. Grafen, egrilme, kirisma ve katlanma veya bunlarin en az ikisinin bir kombinasyonu içinden seçilen herhangi birinin olusumunu sergileyen alti atom halkali bal petegi benzeri bir lamel yapiya sahip olabilir. Grafenin Iamel yapisinin bir mikro-yapisi, tipik olarak bir transmisyon elektron mikroskobu veya bir taramali elektron mikroskobu olabilen bir elektron mikroskobu araciligiyla gözlemlenebilir ve elde edilebilir. Mevcut bulusta spesifik grafen, viskoz lif içinde kullanilir ve yukaridaki optimizasyon, hazirlama yöntemine yönelik olarak gerçeklestirilir. Elde edilen viskoz lif, 0.80'den daha büyük ve daha çok tercihen O.88"den daha büyük olan saptanmis bir uzak kizilötesi normal yayma kuvvetine sahiptir. Düzenlemelerin Detayli Açiklamasi Mevcut bulusta kullanilan grafen, 15 katmandan daha fazla olmayan, tercihen 10 katmandan daha fazla olmayan grafendir. Mevcut bulus ile ilgili bir örnekte, kullanilan grafen, mevcut basvurunun basvuru sahibi tarafindan imal edilir, bu, 3-10 katmana sahiptir ve oksidize edilmemis grafene ait olan selülozun isil islenmesi ile elde edilir. Grafen, gözenekli selülozlar hazirlamak ve elde etmek üzere baslangiç materyalleri olarak misir koçanlarinin alinmasi ve akabinde gözenekli selülozlarin kademeli isitma islemine tabi tutulmasi yoluyla elde edilir. CN 104016341 A, spesifik bir hazirlama yöntemi açiklar. Bir örnekte grafenin hazirlanma yöntemi, asagidaki adimlari içerir: 1) Iignoselülozlar elde etmek üzere misir koçanlarinin bir asit içinde hidrolize edilmesi; 2) gözenekli selülozlar elde etmek üzere lignoselülozlarin bir isleme ajani ile 70 islenmesi, burada kullanilan isleme ajani, bir asit, asit sülfit veya alkali sülfittir, burada asit, tercihen sülfürik asittir, alkali, tercihen, kalsiyum hidroksit, sodyum hidroksit, amonyum hidroksit veya magnezyum hidroksittir ve sülfit, tercihen, kalsiyum sülfit, magnezyum sülfit, sodyum sülfit veya amonyum sülfittir; 3) gözenekli selülozlarin, ferrik klorid, ferröz klorid, ferrik nitrat, ferröz nitrat, ferrik sülfat, ferröz sülfat, potasyum ferrisiyanür, potasyum ferrosiyanür, potasyum trioksalatoferrat, kobalt klorid, kobalt nitrat, kobalt sülfat, kobalt asetat, nikel klorid, nikel nitrat, nikel sülfat ve nikel asetat içinden seçilen bir katalizör ile islenmesi, burada bir isleme sicakligi 50 °C -150 °C, tercihen 80 °C- 120 °C'dir; 4) önceki adimda elde edilen gözenekli selülozlarin, bir grafen prekürsörü saglayacak termal izolasyona yönelik olarak oksijensiz bir ortamda arka arkaya 1000 °C'ye yerlestirilmesi; ) nihai ürün olan grafeni elde etmek üzere grafen prekürsörünün sirasiyla olmak üzere alkali, asit ve su ile yikanmasi. Yukarida bahsedilen yöntemde misir koçanlari kullanilmasina ragmen, teorik olarak ayni zamanda diger bitki kaynaklarindan faydalanilmasinin mümkün oldugu, bu nedenle diger bitki kaynaklarinin mevcut bulus disinda birakilmadigi sonucuna Mevcut bulusa göre, uzak kizilötesi ve antibakteriyel fonksiyonlara sahip viskoz lif elde etmek üzere viskoz içine grafen eklenir. Grafen miktari, viskoz içindeki d-selüloz tercihen %0.3-0.5'Ini asmaz. Mevcut bulusta kullanilan viskoz, önceki teknikte iyi bilinen bir viskozdur ve bunun hazirlanma yöntemi, burada belirtildigi sekildedir: ham materyaller olarak alinan hamurlarin, emprenye, sikistirma, ezme, eskitme, ksantasyon, çözme, olgunlastirma, filtreleme, köpükten arindirma ve benzeri gibi prosedürlere tabi tutulmasi. Hamurlar, yaklasik olarak %18 aköz bir sodyum hidroksit solüsyonu içinde emprenye edilir, bu sekilde selülozlar, alkali selülozlara dönüstürülür, hemiselülozlar çözülerek birakilir ve polimerizasyon derecesi kismen azalir; fazla alkalin solüsyonu akabinde sikistirma yoluyla uzaklastirilir. AIkaIi selüloz topaklari, bir pülverizatör yoluyla ezildikten sonra gevsek yumaklar haline gelir. Yüzey alaninin artmasi nedeniyle, takip eden kimyasal reaksiyonun tek biçimliligi artar. Oksijenin etkisi altinda alkali selülozlar için oksidatif ayrisma gerçeklesir, bu, ortalama polimerizasyon derecesinde azalma ile sonuçlanir ve bu proses, eskitme olarak adlandirilir. Eskitme sonrasinda selüloz ksantat elde etmek üzere alkali selülozlar ile karbon disülfit arasindaki reaksiyon, ksantasyondur, bu, makromoleküller arasindaki hidrojen baglarini daha fazla zayiflatir. Ksantat grubunun hidrofilisitesi nedeniyle, selüloz ksantatlarin seyreltik alkalin solüsyonu içinde çözünürlügü önemli ölçüde gelistirilmis olur. Viskoz yalnizca kati selüloz ksantatlarin seyreltik alkalin solüsyonu içinde çözülmesi yoluyla elde edilir. Yeni hazirlanan viskozdaki nispeten yüksek viskozite ve tuzluluk nedeniyle bunun sekil almasi kolay degildir. Buna uygun olarak bunun belirli bir süre boyunca belirli bir sicaklikta tutulmasi gereklidir, bu olgunlastirma olarak adlandirilir, bu sekilde viskoz içindeki sodyum selüloz ksantatlar kademeli olarak hidrolize edilir ve sabunlastirilir, esterifikasyon derecesi azaltilir ve bir elektrolitin etkilerine karsi viskozite ile birlikte stabilite de bu noktada degisir. Olgunlastirmanin ardindan, köpükleri ve safsizliklari uzaklastirmak üzere köpükten arindirma ve filtreleme gerçeklestirilmesi gerekir. Genel olarak örnegin, ezme öncesinde, eskitme öncesinde, ksantasyon öncesinde veya olgunlastirma öncesinde viskozun hazirlanmasina yönelik olarak yukarida bahsedilen adimlarin birçogunda grafen eklenebilir. Grafen genel olarak filtreleme veya köpükten arindirma ardindan eklenmez. Tercihen mevcut bulusta grafen, olgunlastirma ardindan ve filtreleme öncesinde eklenir. Bulus sahibi, grafenin bu sürede eklenmesi halinde karistirma verimliligi daha yüksek oldugunu, sonuç olarak karistirma süresinin yarisindan daha fazlasi azaltilabilir ve karistirma süresinin üçte ikisi genel olarak azaltilabilir oldugunu bulmustur. Mevcut bulusta tercihen grafen ilk olarak bir dagilma sistemi içine hazirlanir ve akabinde dagilan solüsyon, viskoz ile birlikte dengeli sekilde karistirilir. Tercih edilebilir bir dagilmis solvent, sudur. Tercihen grafen, %0.1-1'lik bir kati içerigine sahip bir dagilma sistemi içine hazirlanir. Baska bir tercih edilebilir yol, ilk olarak grafenin selüloz ksantatlari çözmek üzere kullanilan seyreltik bir alkalin solüsyonu içinde dagitilmasidir ve dagitma islemi sonrasinda, ksantatli selülozlar, diger bir ifadeyle selüloz ksantatlar eklenir. Bu yöntemin avantaji, grafenin eklenmesi nedeniyle ilave suyun eklenmesine gerek bulunmamasi, selülozlarin çözülmenin hemen ardindan grafene baglanmasi, sonuç olarak daha tek biçimli bir karisim olusturulmasidir. Bu tür bir düzenlemede, grafen seyreltik alkalin solüsyonu içinde dagitildiginda ve selüloz ksantatlar eklendikten sonra uzun bir süre boyunca karistirma gerekli degildir. Olgunlastirma sonrasinda yalnizca kisa süreli bir karistirma etkili olabilir, bu, grafenin dagilma verimliligini önemli ölçüde arttirabilir. Daha sonra çekme, filtreleme ve köpükten arindirma ardindan kükürtten arindirma, su ile yikama, yaglama ve kurutma yoluyla nihai viskoz lifler elde edilir. Bunlar klasik yöntemlerdir ve burada detayli olarak açiklanmayacaktir. Örnek 1-Grafenin Hazirlanisi Misir koçanlari, Iignoselülozlar elde etmek üzere 10 dakika boyunca 90 °C'de sülfürik asitler içinde hidrolize edilmistir, burada sülfürik asit kütlesi, misir koçaninin kütlesinin oraninda karistirilan sülfürik asit ve magnezyum sülfidi içeren bir isleme ajani ile islenmistir, burada kullanilan sülfürik asit kütlesi, Iignoselüloz kütlesinin %4'üdür. Gözenekli selülozlar, hidrojen peroksit kullanilarak agartilmistir, burada kullanilan hidrojen peroksit kütlesi, gözenekli selüloz kütlesinin %5'idir ve hidrojen peroksit ile agartma islemi, 5 saat boyunca 100 °Cyde gerçeklestirilmistir. Yukarida elde edilen gözenekli selülozlar ile magnezyum kloridin karisimi, katalize edici bir islem uygulamak üzere 2 saat boyunca 20 °C'de karistirilmistir, burada manganez klorid ila gözenekli selülozun bir kütle orani, 0.01 :1'dir; katalize edici islem ardindan elde edilen ürün, birinci ara ürünü agirlikça %10'dan daha az bir su içerigi ile elde etmek üzere 70 °C'de kurutulmustur. Birinci ara ürün, bir karbonlastirma firinina yerlestirilmistir, karbonlastirma firinina koruyucu bir gaz olarak 200 mL/dakikalik bir gaz besleme hizinda nitrojen beslenmistir ve birinci ara ürün, 5 °C/dakikalik bir hizda 25 °C'den 300 °C'ye isitilmis ve ikinci ara ürünü saglamak üzere 4 saat boyunca inkübe edilmistir; ikinci ara ürün, 20 °C/dakikalik bir hizda 300 °C`den 800 °C'ye isitilmistir ve üçüncü ara ürünü elde etmek üzere 3.5 saat boyunca inkübe edilmistir; üçüncü ara ürün 50 °C/dakikalik bir hizda 800 °C'den 1100 °C'ye isitilmistir ve dördüncü ara ürünü saglamak üzere 6 saat boyunca inkübe edilmistir; dördüncü ara ürün 30 °C/dakikalik bir hizda 1100 °C'den 900 °C'ye sogutulmustur ve 2 saat boyunca inkübe edilmistir; sicaklik azaltimi akabinde dördüncü ara ürün, 60 °C'ye sogutulmustur. Yukarida bahsedilen sogutulmus dördüncü ara ürün, birinci yikanmis ürünü elde etmek üzere 4 saat boyunca 60 °C'de agirlikça %3 aköz bir sodyum hidroksit solüsyonu içinde yikanmistir; 70 °Clde birinci yikanmis ürün, ikinci yikanmis ürünü elde etmek üzere 4 saat boyunca 60 °C'de agirlikça %4 aköz bir hidroklorik asit solüsyonu içinde yikanmistir; ikinci yikanmis ürün, nötrlesene kadar distile su ile yikanmistir ve akabinde grafen elde etmek üzere kurutulmustur. Örnek 2-Viskoz Lifin Hazirlanisi Ham materyaller olarak alinan linterler, viskozu %8'Iik bir kati içerigi ile elde etmek üzere emprenye, alkalizasyon, sikistirma, ezme, eskitme, ksantasyon, çözme ve olgunlastirmaya tabi tutulmustur; Örnek 1'de elde edilen grafen, kütlesi grafenin 5 kati olan su ile dagitilmistir ve akabinde grafen içerikli dagilmis solüsyon, viskoz ile harmanlanmistir ve 1 saat boyunca yüksek hizli bir çalkalayici ile karistirilarak harmanlanmis bir solüsyon olusturulmustur, burada kullanilan grafen miktari, selüloz kütlesinin %0.1`idir. Grafen viskoz lifler, filtreleme ve köpükten arindirma, ardindan çekme, kükürtten arindirma, su ile yikama ve kurutma yoluyla elde edilmistir. Spesifik olarak bir pihtilasma banyosu, 105 g/L sülfürik asit, 200 g/L sodyum sülfat ve 12 g/L çinko sülfattan olusur. Elde edilen grafen viskoz lifler, 0.85'lik bir uzak kizilötesi normal yayma kuvvetine ve Staphylo/occus aureusla karsi %85'Iik bir inhibe etme orani ile birlikte antibakteriyel ve bakteriyostatik aktiviteye sahiptir. Örnek 3-Viskoz Lifin Hazirlanisi Ksantatli linter selülozlar, seyreltik bir sodyum hidroksit solüsyonu içinde çözülmüstür, burada Örnek 1`de elde edilen grafen, önceden seyreltik sodyum hidroksit solüsyonuna eklenmistir. Olgunlastirma sonrasinda %8'lik bir kati içerigine sahip bir viskoz hazirlanmistir ve elde edilmistir, bu, yarim saat boyunca yüksek hizli bir çalkalayici ile karistirilmistir, burada kullanilan grafen miktari, selüloz kütlesinin %0.6'sidir. Grafen viskoz lifler, filtreleme ve köpükten arindirma, ardindan çekme, kükürtten arindirma, su ile yikama ve kurutma yoluyla hazirlanmis ve elde edilmistir. Spesifik olarak bir pihtilasma banyosu, 105 g/L sülfürik asit, 200 g/L sodyum sülfat ve 12 g/L çinko sülfattan olusur. Elde edilen grafen viskoz lifler, 0.88'lik bir uzak kizilötesi normal yayma kuvvetine ve Staphy/o/occus aureus'a karsi %95'Iik bir inhibe etme orani ile birlikte antibakteriyel ve bakteriyostatik aktiviteye sahiptir. Örnek 4-Viskoz Lifin Hazirlanisi Ham materyaller olarak misir koçanlari ile ksantatli misir koçani selülozlar, seyreltik bir sodyum hidroksit solüsyonu içinde çözülmüstür, burada Örnek 1'de elde edilen grafen, önceden seyreltik sodyum hidroksit solüsyonuna eklenmistir. Olgunlastirma sonrasinda yarim saat boyunca yüksek hizli bir çalkalayici ile karistirilmistir, burada grafen miktari, selüloz kütlesinin %1'idir. Misir koçani viskoz selülozlar, filtreleme ve köpükten arindirma, ardindan çekme, kükürtten arindirma, su ile yikama ve kurutma yoluyla hazirlanmis ve elde edilmistir. Spesifik olarak bir pihtilasma banyosu, 105 g/L sülfürik asit, 200 g/L sodyum sülfat ve 12 g/L çinko sülfattan olusur. Elde edilen misir koçani viskoz lifler, 0.90'lik bir uzak kizilötesi normal yayma kuvvetine ve Staphy/oloccus aureus'a karsi %97'lik bir inhibe etme orani ile birlikte antibakteriyel ve bakteriyostatik aktiviteye sahiptir. Kontrol Örnegi 1 Ham materyaller olarak alinan Iinterler, viskozu %8'lik bir kati içerigi ile elde etmek üzere emprenye, alkalizasyon, sikistirma, ezme, eskitme, ksantasyon, çözme ve olgunlastirmaya tabi tutulmustur ve viskoz, yarim saat boyunca yüksek hizli bir çalkalayici ile karistirilmistir. Grafen viskoz lifler, filtreleme ve köpükten arindirma, ardindan çekme, kükürtten arindirma, su ile yikama ve kurutma yoluyla elde edilmistir. Spesifik olarak bir pihtilasma banyosu, 105 g/L sülfürik asit, 200 g/L sodyum sülfat ve 12 g/L çinko sülfattan olusur. Elde edilen grafen viskoz lifler, 0.70'Iik bir uzak kizilötesi normal yayma kuvvetine ve Staphyloloccus aureus'a karsi %20'Iik bir inhibe etme orani ile birlikte antibakteriyel ve bakteriyostatik aktiviteye sahiptir. Kontrol Örnegi 2 Ham materyal olarak grafitin alinmasi ile bir grafen hazirlamaya yönelik bir yöntem, asagidaki adimlari içerir: 1) 5 g'lik grafit pulu ile 150 mL'Iik konsantre sülfürik asit içeren bir karistirilmis solüsyona 50 mL'Iik konsantre nitrik asit eklenmesi, karisimin normal sicaklikta 24 saat boyunca karistirilmasi, deiyonize su ile üç kez yikanmasi, bir grafit ara katki bilesigi elde etmek üzere 60 °C'de kurutulmasi; 2) genlesmis grafit saglamak üzere yukarida elde edilen grafit ara katki bilesiginin 30 saniye boyunca 1050 °C'de hizli sekilde genlestirilmesi; 3) yukarida elde edilen 0.39`Iik genlestirilmis grafit ile 60 mL'Iik konsantre sülfürik asit karisimina yavasça 3 g'lik potasyum permenganat eklenmesi, bunun 24 saat boyunca 60 °C'de karistirilmasi, bir buz banyosu içine 60 mL'Iik deiyonize su ile 15 mL'Iik hidrojen peroksit eklenmesi, oksidize edilmis bir grafen elde etmek üzere karisimin nötrlesene kadar yikanmasi; 4) yukarida elde edilen oksidize edilmis grafenin su içinde dagitilmasi, oksidize edilmis grafenin santrifüjleme yoluyla ayrilmasi; Üst Faz 1 ile Çökelti 1'i saglamak üzere 40 dakikalik bir süre boyunca 8000 rmp"lik bir dönüs hizinda santrifüjleme gerçeklestirimesi, burada elde edilen Üst Faz 1, yalnizca küçük boyutlu, oksidize edilmis grafendir; Üst Faz 1'in dagitilmasi, oksidize edilmis grafenin bir transfer baski prosesi araciligiyla bir polietilen tereftalat plastik (PET) substrat üzerine aktarilmasi, bu, grafeni elde etmek üzere 50 dakika boyunca 60 °C'de hidroiyodik asit ile indirgenmistir. Ksantatli misir koçani selülozlar, seyreltik bir sodyum hidroksit solüsyonu içinde çözülmüstür, burada yukarida bahsedilen oksidasyon indirgeme yöntemi ile hazirlanan ve elde edilen grafen, daha önce seyreltik sodyum hidroksit solüsyonuna eklenmistir. Olgunlastirma sonrasinda %10'Iuk bir kati içerigine sahip bir viskoz hazirlanmistir ve elde edilmistir, bu, yarim saat boyunca yüksek hizli bir çalkalayici ile karistirilmistir, burada kullanilan grafen miktari, selüloz kütlesinin %1lidir. Grafen viskoz lifler, filtreleme ve köpükten arindirma, ardindan çekme, kükürtten arindirma, su ile yikama ve kurutma yoluyla hazirlanmis ve elde edilmistir. Spesifik olarak bir pihtilasma banyosu, 105 g/L sülfürik asit, 200 g/L sodyum sülfat ve 12 g/L çinko sülfattan olusur. Elde edilen grafen viskoz lifler, 0.80*Iik bir uzak kizilötesi normal yayma kuvvetine ve Staphy/oloccus aureus"a karsi %50`lik bir inhibe etme orani ile birlikte antibakteriyel ve bakteriyostatik aktiviteye sahiptir. Spesifik olarak kizilötesi test verileri, FZ/T64010-2000 test yöntemine göre Çin Ulusal Tekstil Denetim Test Merkezi tarafindan test edilmistir. Denetim Test Merkezi tarafindan test edilmistir. Mevcut bulusta basvuru sahibi tarafindan hazirlanan grafen, viskoz liflerin hazirlanmasinda kullanilmistir, bu, önceki teknikte herhangi bir benzer etki gözlemlenmis olmamasina ragmen mevcut viskoz liflerin uzak kizil ötesi özelliklerini ve antibakteriyel özelliklerini önemli ölçüde gelistirmistir. TR TR TR TR TR TRPRODUCTION PROCESS OF GRAPHENE-CONTAINING VISCOSE FIBERS Technical Field The present invention relates to a viscose fiber and the process for its preparation, and specifically to a graphene-containing viscose fiber and the process for its preparation. Sub-Basis of the Technique Viscose fiber is generally prepared from raw materials such as liner, corn cob, wood, and small amounts of natural celluloses such as bamboo, which undergo a series of processes such as cooking, bleaching, etc., to prepare a dissolution pulp with a relatively high cellulose purity, followed by impregnation, compression, crushing, aging, xanthation, dissolution, mixing, filtering, defoaming, filtering, drawing, further processing, drying, packaging, etc. Currently, viscose fiber is mostly used as a textile fiber. CN 103046151 A describes a graphene-blended, improved cellulose fiber prepared by mixing an oxidized graphene solution with an improved cellulose solution, molding the mixture via a viscous wet spinning process, and subsequently reducing the mixture. The viscous fiber obtained by this method has slightly improved strength, with a dry breaking strength of up to 2.62 cN/dtex and a wet breaking strength of 1.54 cN/dtex. Furthermore, the related components demonstrate the effect of graphene in increasing fiber strength. CN 103556275 A describes a far-infrared bamboo charcoal viscous fiber and its preparation method. This invention aims to develop a far-infrared bamboo charcoal viscose fiber, which is not currently available in existing techniques, and to address the problem of poor drawability of bamboo charcoal viscose fibers. The fiber is characterized by a far-infrared ceramic powder content of 1-10% by weight, a bamboo charcoal content of 0.1-10% by weight, a far-infrared emissivity greater than 80%, an ammonia absorption rate not less than 50%, a permeability not less than 500 mm/s, and a color fastness to washing of grade 4. This invention provides a far-infrared bamboo charcoal viscose fiber and its preparation method. The present invention presents far-infrared bamboo charcoal viscose fiber with heat insulation effects, along with radiant far-infrared rays that have health functions such as activating cellular tissues and promoting blood circulation. Furthermore, it is shown that these described components are obtained by adding ceramic powder. CN 104151515 A describes a graphene-modified furan resin prepared by reacting formaldehyde, furfuryl alcohol, and graphene. The invention provides a method for preparing the graphene-modified furan resin. The graphene-modified furan resin provided by the invention has a high bonding strength; and the bonds between the carbon atoms in graphene are quite flexible, thus the graphene-modified furan resin provided by the invention has high durability. CN 103966844 A describes a method for preparing an electrically conductive composite fiber from graphene. The preparation method is simple, acceptable within the process, and easy to implement. This method describes a graphene-based conductive composite fiber that yields high conductivity and anti-radiation performance along with a high reduction ratio. It also provides the preparation processes and applications of these fibers. Description of the Invention: The present invention provides a preparation method for a novel viscous fiber that further enhances the antibacterial and bacteriostatic properties of the viscous fiber, as well as its far-infrared functionality. According to the current findings, the method for preparing a viscose fiber involves: adding graphene in no more than 10 layers to a viscose or semi-processed viscose product, where the graphene is prepared by a method involving the following steps: 1) hydrolyzing corn cobs in an inorganic acidic aqueous solution to obtain lignocelluloses; 2) processing the lignocelluloses with a processing agent at 70 °C-180 °C to provide porous celluloses, where the processing agent used is an acid, acid sulfide, or alkali sulfide; 3) Treatment of porous celluloses with a catalyst selected from a group consisting of ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium trioxalatoferrate, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate, and nickel acetate, where a processing temperature of 50 °C-150 °C is maintained; 4) The porous celluloses obtained in the previous step are successively placed at 1000 °C in an oxygen-free environment for thermal insulation to provide a graphene precursor; 5) The graphene precursor is washed sequentially with alkali, acid, and water to obtain the final product, graphene. Preferably, step 2) in the method, the processing agent used, is selected from a group consisting of sulfuric acid, calcium hydroxide, sodium hydroxide, ammonium hydroxide or magnesium hydroxide, calcium sulfite, magnesium sulfite, sodium sulfite or ammonium sulfite. Preferably, the amount of graphene added is 0.05–1.0% of the mass of α-cellulose in the viscose, more preferably 0.2–0.8% of the mass of ε-cellulose in the viscose. The raw materials used in the present invention for the preparation of graphene are derived from biomass, and biomass sources are selected from vegetables and/or agricultural and forestry wastes, or a combination of at least two of these, preferably coniferous, broadleaf, deciduous trees and agricultural and forestry wastes, or a combination of at least two of these; Agricultural and forestry wastes are preferably selected from corn stalks, corn cobs, sorghum stalks, sugar beet pulp, bagasse, furfural residue, xylose residue, sawdust, cotton stalks, hulls and cane, or a combination of at least two of these, and preferably from corn cobs currently available on the public market. Biomass raw materials, especially graphene prepared from corn cobs, exhibit porosity at the microcosmic level, thus increasing the specific surface area, particularly in the case of graphene prepared by the applicant. In a preferred arrangement, the preparation of the viscose involves the steps of impregnation, compression, crushing, aging, xanthematization, dissolution, maturation, filtration and defoaming, where the graphene is added prior to filtration. Additionally, graphene is first prepared into a dispersion system, where the dispersing solvent is water and the solid content of the dispersion system is 0.1–1%. Another preferred arrangement for preparing the viscose involves the steps of impregnation, compression, crushing, aging, xanthate, dissolution, maturation, filtration, and defoaming, where graphene is added during the dissolution step and pre-dispersed in a dilute alkaline solution used to dissolve cellulose xanthates. The present invention also relates to a viscose fiber containing graphene, where the graphene is not oxidized graphene. Unoxidized graphene specifically means graphene that has not been prepared and obtained by an oxidation-reduction method, or graphene whose preparation process does not include an oxidation step. Graphene can have a six-atom ring-like honeycomb structure exhibiting the formation of bending, wrinkling, and folding, or at least a combination of these. A microstructure of the graphene lamellar structure can be observed and obtained via an electron microscope, typically a transmission electron microscope or a scanning electron microscope. In the present invention, the specific graphene is used in a viscous fiber, and the above optimization is performed with regard to the preparation method. The resulting viscous fiber has a determined far-infrared normal emissivity greater than 0.80 and preferably greater than 0.88. Detailed Description of the Arrangements The graphene used in the present invention is graphene with no more than 15 layers, preferably no more than 10 layers. In an example related to the present invention, the graphene used is manufactured by the applicant of the present application, which has 3-10 layers and is obtained by heat treatment of cellulose belonging to unoxidized graphene. Graphene is obtained by taking corn cobs as starting materials to prepare and obtain porous celluloses and subsequently subjecting the porous celluloses to a stepwise heating process. CN 104016341 A describes a specific preparation method. In an example, the method of preparing graphene is... The process involves the following steps: 1) hydrolyzing corn cobs in an acid to obtain lignocelluloses; 2) processing the lignocelluloses with a processing agent to obtain porous celluloses, where the processing agent used is an acid, acid sulfide, or alkali sulfide, where the acid is preferably sulfuric acid, the alkali is preferably calcium hydroxide, sodium hydroxide, ammonium hydroxide, or magnesium hydroxide, and the sulfide is preferably calcium sulfite, magnesium sulfite, sodium sulfite, or ammonium sulfite; 3) treating the porous celluloses with ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulfate, ferrous sulfate, potassium ferricyanide, potassium ferrocyanide, potassium trioxalatoferrate, cobalt chloride, cobalt nitrate, cobalt 3) treatment with a catalyst selected from sulfate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulfate and nickel acetate, where a processing temperature is 50 °C -150 °C, preferably 80 °C-120 °C; 4) successive placement of the porous celluloses obtained in the previous step at 1000 °C in an oxygen-free environment for thermal insulation to provide a graphene precursor; 5) washing of the graphene precursor with alkali, acid and water respectively to obtain the graphene, which is the final product. Although corn cobs are used in the above-mentioned method, it is theoretically possible to utilize other plant sources as well, therefore, other plant sources are not excluded from the present invention. According to the present invention, viscose fiber with far infrared and antibacterial functions. Graphene is added to the viscose to obtain the desired result. The amount of graphene preferably does not exceed 0.3-0.5% of the d-cellulose in the viscose. The viscose used in the present invention is a viscose well known in previous techniques, and its preparation method is as described here: the pulps taken as raw materials are subjected to procedures such as impregnation, compression, crushing, aging, xanthematization, dissolution, maturation, filtering, defoaming, and so on. The pulps are impregnated in an aqueous sodium hydroxide solution of approximately 18%, in which case the celluloses are converted into alkali celluloses, the hemicelluloses are left dissolved, and the degree of polymerization is partially reduced; the excess alkaline solution is subsequently removed by compression. The alkali cellulose pellets are then crushed by means of a pulverizer, resulting in loose pulp. They form clumps. Due to the increase in surface area, the uniformity of the subsequent chemical reaction increases. Under the influence of oxygen, oxidative decomposition occurs for alkali celluloses, which results in a decrease in the average degree of polymerization, and this process is called aging. The reaction between alkali celluloses and carbon disulfide to obtain cellulose xanthate after aging is xanthate, which further weakens the hydrogen bonds between macromolecules. Due to the hydrophilicity of the xanthate group, the solubility of cellulose xanthates in dilute alkaline solution is significantly improved. Viscous is obtained only by dissolving solid cellulose xanthates in dilute alkaline solution. Due to the relatively high viscosity and salinity of the newly prepared viscose, it is not easy to shape. Accordingly, it is necessary to keep it at a certain temperature for a certain period of time. This is called maturation, in which the sodium cellulose xanthates in the viscose are gradually hydrolyzed and saponified, the degree of esterification is reduced, and stability, along with viscosity, changes at this point against the effects of an electrolyte. Following maturation, defoaming and filtration are necessary to remove foams and impurities. In general, graphene can be added in many of the aforementioned steps for the preparation of the viscose, for example, before crushing, before aging, before xanthenation, or before maturation. Graphene is generally not added after filtration or defoaming. Preferably, in the present invention, graphene is added after maturation and before filtration. The inventor claims that mixing efficiency is higher when graphene is added at this time, consequently the mixing time can be reduced by more than half, and two-thirds of the mixing time can be reduced overall. It has been found that it can be reduced as follows. In the present invention, graphene is preferably first prepared into a dispersion system, and then the dispersed solution is mixed evenly with the viscous solvent. A preferred dispersed solvent is water. Preferably, graphene is prepared into a dispersion system with a solid content of 0.1-1%. Another preferable method is to first disperse the graphene in a dilute alkaline solution used to dissolve cellulose xanthates, and after the dispersion process, xanthate celluloses, in other words cellulose xanthates, are added. The advantage of this method is that there is no need to add additional water because of the addition of graphene, the celluloses bind to the graphene immediately after dissolution, resulting in a more uniform mixture. In this type of arrangement, when graphene is dispersed in a dilute alkaline solution and After the addition of cellulose xanthates, prolonged stirring is not necessary. Only short stirring after maturation may be effective, which can significantly increase the dispersion efficiency of graphene. The final viscose fibers are then obtained through drawing, filtration and defoaming, followed by desulfurization, water washing, oiling and drying. These are classical methods and will not be described in detail here. Example 1 - Preparation of Graphene: Corn cobs were hydrolyzed in sulfuric acid at 90 °C for 10 minutes to obtain lignocelluloses, where the sulfuric acid mass was treated with a processing agent containing sulfuric acid and magnesium sulfide mixed in proportion to the mass of corn cobs, where the sulfuric acid mass used was 4% of the lignocellulose mass. Porous celluloses were bleached using hydrogen peroxide, where the mass of hydrogen peroxide used was 5% of the mass of porous cellulose, and the bleaching process with hydrogen peroxide was carried out at 100 °C for 5 hours. A mixture of the obtained porous celluloses with magnesium chloride was stirred at 20 °C for 2 hours to apply a catalytic process, where the mass ratio of manganese chloride to porous cellulose was 0.01:1; the product obtained after the catalytic process was dried at 70 °C to obtain the first intermediate with a water content of less than 10% by weight. The first intermediate was placed in a carbonization furnace, the carbonization furnace was fed with nitrogen as a protective gas at a gas feed rate of 200 mL/min, and the first intermediate... The product was heated from 25 °C to 300 °C at a rate of 5 °C/min and incubated for 4 hours to yield the second intermediate; the second intermediate was heated from 300 °C to 800 °C at a rate of 20 °C/min and incubated for 3.5 hours to obtain the third intermediate; the third intermediate was heated from 800 °C to 1100 °C at a rate of 50 °C/min and incubated for 6 hours to yield the fourth intermediate; the fourth intermediate was cooled from 1100 °C to 900 °C at a rate of 30 °C/min and incubated for 2 hours; following the temperature reduction, the fourth intermediate was cooled to 60 °C. The aforementioned cooled fourth intermediate product was washed for 4 hours at 60 °C in a 3% by weight aqueous sodium hydroxide solution to obtain the first washed product; at 70 °C, the first washed product was washed for 4 hours at 60 °C in a 4% by weight aqueous hydrochloric acid solution to obtain the second washed product; the second washed product was washed with distilled water until neutralized and subsequently dried to obtain graphene. Example 2 - Preparation of Viscous Fiber The linters taken as raw materials were subjected to impregnation, alkalization, compression, crushing, aging, xanthematization, dissolution and maturation to obtain viscosity with an 8% solid content; the graphene obtained in Example 1 was dispersed with water whose mass is 5 times that of graphene and subsequently... A dispersed graphene-containing solution was blended with viscose and mixed for 1 hour with a high-speed shaker to create a blended solution, where the amount of graphene used is 0.1% of the cellulose mass. Graphene viscose fibers were obtained by filtration and defoaming, followed by drawing, desulfurization, water washing, and drying. Specifically, a coagulation bath consisted of 105 g/L sulfuric acid, 200 g/L sodium sulfate, and 12 g/L zinc sulfate. The resulting graphene viscose fibers have antibacterial and bacteriostatic activity with a far-infrared normal emission strength of 0.85 and an inhibition rate of 85% against Staphylococcus aureus. Example 3 - Preparation of Viscose Fiber Xanthate linter cellulose was dissolved in a dilute sodium hydroxide solution, where the graphene obtained in Sample 1 was previously added to the dilute sodium hydroxide solution. After maturation, a viscous fiber with an 8% solid content was prepared and obtained, which was mixed with a high-speed shaker for half an hour, where the amount of graphene used was 0.6% of the cellulose mass. Graphene viscose fibers were prepared and obtained by filtration and defoaming, followed by drawing, desulfurization, washing with water, and drying. Specifically, a coagulation bath consisted of 105 g/L sulfuric acid, 200 g/L sodium sulfate, and 12 g/L zinc sulfate. The resulting graphene viscose fibers were then processed. It has antibacterial and bacteriostatic activity with a normal far-infrared emission power of 0.88 and an inhibition rate of 95% against Staphylococcus aureus. Example 4 - Preparation of Viscous Fiber As raw materials, corn cobs and xanthate corn cob celluloses were dissolved in a dilute sodium hydroxide solution, where the graphene obtained in Example 1 was added to the dilute sodium hydroxide solution beforehand. After maturation, it was mixed with a high-speed shaker for half an hour, where the amount of graphene is 1% of the cellulose mass. Corn cob viscous celluloses were prepared and obtained by filtration and defoaming, followed by drawing, desulfurization, washing with water and drying. Specifically, a coagulation bath, The solution consists of 105 g/L sulfuric acid, 200 g/L sodium sulfate, and 12 g/L zinc sulfate. The resulting corn cob viscose fibers have antibacterial and bacteriostatic activity with a far-infrared normal emission strength of 0.90 and an inhibition rate of 97% against Staphylococcus aureus. Control Sample 1: The liners taken as raw materials were subjected to impregnation, alkalization, compression, crushing, aging, xanthenation, dissolution, and maturation to obtain viscose with an 8% solid content, and the viscose was mixed with a high-speed shaker for half an hour. Graphene viscose fibers were obtained by filtration and defoaming, followed by drawing, desulfurization, water washing, and drying. Specifically, a coagulation bath consists of 105 g/L sulfuric acid, 200 g/L sodium sulfate, and 12 g/L zinc sulfate. The resulting graphene viscous fibers have antibacterial and bacteriostatic activity with a far-infrared normal emission strength of 0.70 and an inhibition rate of 20% against Staphylococcus aureus. Control Sample 2 A method for preparing graphene using graphite as raw material involves the following steps: 1) Adding 50 mL of concentrated nitric acid to a mixed solution containing 5 g of graphite flakes and 150 mL of concentrated sulfuric acid, stirring the mixture at normal temperature for 24 hours, washing it three times with deionized water, and adding a graphite intermediate. 1) Drying at 60 °C to obtain the compound; 2) Rapidly expanding the graphite interlayer compound obtained above at 1050 °C for 30 seconds to provide expanded graphite; 3) Slowly adding 3 g of potassium permenganate to a mixture of 0.39% expanded graphite and 60 mL of concentrated sulfuric acid, stirring at 60 °C for 24 hours, adding 60 mL of deionized water and 15 mL of hydrogen peroxide to an ice bath, washing the mixture until neutralized to obtain oxidized graphene; 4) Dispersing the oxidized graphene obtained above in water, separating the oxidized graphene by centrifugation; To obtain Phase 1 and Precipitate 1, centrifugation was performed for 40 minutes at a rotation speed of 8000 rpm, resulting in Upper Phase 1, which is only small-sized, oxidized graphene; dispersion of Upper Phase 1, transfer of the oxidized graphene onto a polyethylene terephthalate plastic (PET) substrate via a transfer printing process, which was then reduced with hydroiodic acid at 60 °C for 50 minutes to obtain graphene. Xanthate corn cob celluloses were dissolved in a dilute sodium hydroxide solution, where the graphene prepared and obtained by the aforementioned oxidation-reduction method was added to the dilute sodium hydroxide solution. After maturation, a viscous fiber with a 10% solid content was prepared and obtained, which was mixed for half an hour with a high-speed shaker, where the amount of graphene used was 1% of the cellulose mass. Graphene viscose fibers were prepared and obtained by filtration and defoaming, followed by drawing, desulfurization, washing with water, and drying. Specifically, a coagulation bath consisted of 105 g/L sulfuric acid, 200 g/L sodium sulfate, and 12 g/L zinc sulfate. The resulting graphene viscose fibers possess antibacterial and bacteriostatic activity with a normal far-infrared emission strength of 0.80* and an inhibition rate of 50% against Staphylococcus aureus. Specifically, infrared test data were obtained by the China National Textile Supervision and Testing Center according to the FZ/T64010-2000 test method. In the present invention, graphene prepared by the applicant was used in the preparation of viscose fibers, which significantly improved the far-infrared and antibacterial properties of the existing viscose fibers, although no similar effect was observed in previous techniques.

Claims (5)

ISTEMLER . Bir viskoz lif hazirlanmasina yönelik bir yöntem olup, özelligi yöntemin asagidakileri içermesi ile karakterize edilmesidir: bir viskoza veya yari islenmis bir viskoz ürününe 10 katmandan daha fazla olmayan bir grafen eklenmesi, burada eklenen grafen, oksidize edilmemis bir grafendir, burada grafen, asagidakileri içeren bir yöntem araciligiyla hazirlanir:CLAIMS. A method for preparing a viscose fiber, characterized in that the method comprises: adding not more than 10 layers of graphene to a viscose or a semi-processed viscose product, wherein the added graphene is non-oxidized graphene, wherein the graphene is prepared by a method comprising: 1) Iignoselülozlar elde etmek üzere misir koçanlarinin inorganik asidik bir aköz solüsyon içinde hidrolize edilmesi;1) Hydrolyzing corn cobs in an inorganic acidic aqueous solution to obtain ignocelluloses; 2) gözenekli selülozlar saglamak üzere Iignoselülozlarin bir isleme ajani ile 70 °C-180 °C'de islenmesi, burada kullanilan isleme ajani, bir asit, asit sülfit veya alkali sülfittir;2) treating the ignocelluloses with a treating agent at 70 °C-180 °C to provide porous celluloses, wherein the treating agent used is an acid, acid sulphide or alkali sulphide; 3) gözenekli selülozlarin, ferrik klorid, ferröz klorid, ferrik nitrat, ferröz nitrat, ferrik sülfat, ferröz sülfat, potasyum ferrisiyanür, potasyum ferrosiyanür, potasyum trioksalatoferrat, kobalt klorid, kobalt nitrat, kobalt sülfat, kobalt asetat, nikel klorid, nikel nitrat, nikel sülfat ve nikel asetattan olusan grup içinden seçilen bir katalizör ile islenmesi, burada bir Isleme sicakligi 50 °C-1503) treatment of porous celluloses with a catalyst selected from the group consisting of ferric chloride, ferrous chloride, ferric nitrate, ferrous nitrate, ferric sulphate, ferrous sulphate, potassium ferricyanide, potassium ferrocyanide, potassium trioxalatoferrate, cobalt chloride, cobalt nitrate, cobalt sulphate, cobalt acetate, nickel chloride, nickel nitrate, nickel sulphate and nickel acetate, wherein a treatment temperature of 50 °C-150 °C is achieved. 4) önceki adimda elde edilen gözenekli selülozlarin, bir grafen prekürsörü saglayacak termal izolasyona yönelik olarak oksijensiz bir ortamda arka arkaya 1000 °C'ye yerlestirilmesi;4) placing the porous celluloses obtained in the previous step consecutively at 1000 °C in an oxygen-free environment for thermal insulation to provide a graphene precursor; 5) nihai ürün olan grafeni elde etmek üzere grafen prekürsörünün sirasiyla olmak üzere alkali, asit ve su ile yikanmasi. Istem Te göre yöntem olup, özelligi kullanilan grafen miktarinin, viskoz içindeki ci-selüloz kütlesinin %0.05-1.0'i olmasidir. istem 2'ye göre yöntem olup, özelligi grafen miktarinin, viskoz içindeki oi-selüloz kütlesinin %0.2-0.8'i olmasidir. Istem 1'e göre yöntem olup, özelligi 2) adiminin, Iignoselülozlarin bir isleme ajani ile 100 °C-120 °Cide islenmesini içermesidir ve burada kullanilan isleme ajani, sülfürik asit, kalsiyum hidroksit, sodyum hidroksit, amonyum hidroksit veya magnezyum hidroksit, kalsiyum sülfit, magnezyum sülfit, sodyum sülfit veya amonyum sülfitten olusan grup içinden seçilir. istem 1'e göre yöntem olup, özelligi viskozun hazirlanmasinin, bir hamurda emprenye, sikistirma, ezme, eskitme, ksantasyOn, çözme, olgunlastirma, filtreleme ve köpükten arindirma adimlarinin gerçeklestirilmesini içermesidir, burada grafen, filtreleme öncesinde eklenir. istem 17e göre yöntem olup, özelligi viskozun hazirlanmasinin, bir hamurda emprenye, sikistirma, ezme, eskitme, ksantasyon, çözme, olgunlastirma, filtreleme ve köpükten arindirma adimlarinin gerçeklestirilmesini içermesidir, burada grafen, çözme adimi sirasinda eklenir ve grafen, selüloz ksantatlari çözmek üzere kullanilan seyreltik bir alkalin solüsyonu içinde önceden dagitilir.5) Washing the graphene precursor with alkali, acid and water, respectively, to obtain the final product graphene. The method according to claim 1, characterized in that the amount of graphene used is 0.05-1.0% of the mass of ci-cellulose in the viscose. The method according to claim 2, characterized in that the amount of graphene is 0.2-0.8% of the mass of o-cellulose in the viscose. The method according to claim 1, characterized in that step 2) includes treating the ignocelluloses with a treating agent at 100 ° C - 120 ° C, wherein the treating agent used is selected from the group consisting of sulfuric acid, calcium hydroxide, sodium hydroxide, ammonium hydroxide or magnesium hydroxide, calcium sulfite, magnesium sulfite, sodium sulfite or ammonium sulfite. The method according to claim 1, characterised in that the preparation of the viscose comprises carrying out the steps of impregnation, compression, crushing, ageing, xanthation, dissolving, maturation, filtering and defoaming in a pulp, wherein graphene is added before filtering. The method according to claim 17, characterised in that the preparation of the viscose comprises carrying out the steps of impregnation, compression, crushing, ageing, xanthation, dissolving, maturation, filtering and defoaming in a pulp, wherein the graphene is added during the dissolving step and the graphene is pre-dispersed in a dilute alkaline solution used to dissolve cellulose xanthates.
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